JPS58113151A - Diphenylamines and pest-combatting agent containing the same - Google Patents

Abstract

NEW MATERIAL:2', 6'-Dichloro-4'-trifluoromethyl 2, 6-dinitro-3-chloro-4-trifluoromethyldiphenylamine. USE:Pest-combatting agent for agricultural and horticultural purposes. PREPARATION:The reaction between a compound of formulaIand another one of formula II (one of Z<1> and Z<2> are halogen and the other is amino) is conducted in the presence of an acid-binding agent such as potassium hydroxide, preferably in a solvent at -100-200 deg.C for 1-10hr to give the novel substance.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to diphenylamine compounds that exhibit effective activity as pest control agents, and more particularly, to diphenylamine compounds that exhibit effective activity as pest control agents.
The present invention relates to dichloro-4'-trifluoromethyl 2,6-sinitro-3-chloro-4-trifluoromethyldiphenylamine and a pest control agent containing the same as an active ingredient.

The present invention is based on the following findings.

The diphenylamine compound is disclosed in Japanese Patent Application Laid-open No. 54-109.
Although it is included in the compound group represented by the general formula [E] in the specification of No. 931, it is not specifically described in the specification,
It is also a new compound that has not been described in any other literature.

In addition, the diphenylamine compound exhibits an excellent growth-inhibiting effect, especially against harmful agricultural and horticultural pathogens and mites, compared to the compounds specifically described in the specification.

The compound of the present invention is as follows. However, when zl is a halogen atom, l is an amino group, and when z+ is an amino group, z2 is a halogen atom. ) in the presence of an acid binder.

This production method includes a method of reacting aniline represented by the general formula fl) with the general formula (2,6-sinitro 3-10 rho 4-) IJ fluoromethylhalogenobenzene represented by Ill, and a method of reacting the aniline represented by the general formula Formula (1
1 and the general formula (Ill
There are two consecutive methods of reacting 2,6-sinitro, 3-10, and 4-trifluoromethylaniline, but industrially, the former is more desirable than the latter.

The acid binder used in the above reaction is a basic substance, and examples thereof include hydroxides, carbonates, and hydrides of alkali metals, and hydroxides and carbonates of alkaline earth metals. are potassium hydroxide, sodium hydride, sodium hydrogen carbonate, etc.

The above reaction is preferably carried out in the presence of a solvent. Examples of the solvent used include aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran, sulfolane, and dioxane, with dimethylformamide and tetrahydrofuran being preferred. The reaction temperature is generally -1000C to 2.00C, and the reaction time I'i is 0.5 to 24 hours, preferably 1 to 10 hours.

Next, a specific synthesis example will be described.

Synthesis Example Add 2,6-dichloro- to 20 ml of tetrahydrofuran.
4-) 0.9 g of IJ fluoromethylaniline was dissolved, and 0.4 g of 50 g of sodium hydride was added over 10 minutes at 0 to 10° C. under water cooling, followed by stirring at room temperature for 30 minutes. 1.2 g of 2,4-dichloro-3,s-dinitropenztrifluoride was added thereto, and the
A time reaction was performed. The reaction product was poured into water and made weakly acidic with concentrated hydrochloric acid, and the precipitate was filtered and recrystallized from ethanol/water to obtain 2' with a melting point of 127-129°C.

6'-cyclo4'-)IJ fluoromethyl2. 6
-Sinitro 3-10 Low 4-to! 1.1 g of J fluoromethyldiphenylamine was obtained.

The compounds of the present invention are useful as active ingredients of pest control agents. It exhibits antibacterial activity in suppressing and killing harmful bacteria such as Aspergillus, Gibberella, and Penicillium that are prevalent in industrial products, seeds, and fruits during storage.

It also exhibits a growth-suppressing effect on agricultural and horticultural harmful insects and mites, such as the diamondback moth, leafhopper, and red bean weevil, as well as mites such as the two-spotted spider mite, false red spider mite, and citrus spider mite. Furthermore, the compounds of the present invention are effective against harmful agricultural and horticultural diseases, such as rice blast, rice sheath blight, cucumber charcoal spot, cucumber powdery mildew, tomato late blight, citrus black spot, tomato ring spot, apple scab, apple leaf spot leaf disease,
It exhibits a growth-inhibiting effect on pathogenic bacteria such as grape downy mildew, pear black spot, gray mold, and rust. In particular, it shows excellent control effects against harmful agricultural and horticultural pathogens and mites.

When used, it can be formulated into various forms such as emulsions, powders, irrigation agents, and liquids together with agricultural chemical adjuvants, as in the case of conventional agricultural chemical formulations.

When these preparations are actually used, they can be used as they are, or they can be diluted to a predetermined concentration with a diluent such as water.

Examples of the agrochemical adjuvants mentioned herein include solid carriers such as Merck, kaolin, bentonite, diatomaceous earth, white carbon, clay, and powdered powder, water, xylene, toluene, chlorobenzene, and cyclohexyl spreading agents. In addition, if necessary, it can be used in combination with other agricultural chemicals such as insecticides, acaricides, fungicides, plant growth regulators, etc. For example, the fungicides include N-(3t5-dichlorophenyl)-1, 2-dimethylcyclopropane-1,2-
Imides such as dicarboximide, methyl-1
-(Butylcarbamoyl)-2-Benzimidazole carbamate Any benzimidazole type, leave one first leaf of a young French bean seedling, cut off the other leaves, transfer it to a cup, and transfer young and adult two-spotted spider mites to this cup. Approximately 30 primary leaves were inoculated and immersed for 10 seconds in a drug solution prepared by diluting a preparation of the test compound with water to a predetermined concentration. After air-drying, it was placed in a lighted incubator at 28°C, and after 3 days it was determined whether it was alive or dead, and the insecticidal rate was calculated using the following formula.

(2-2) In the above test example (2-1), adult Indian spider mites were released, the adults were removed after spawning, and (11) the hatching status was observed on the 7th day after air drying to determine the ovicidal rate (chip). ) (number of dead eggs/number of laid eggs x 100) was calculated.

Test Example 3 Cucumbers (variety 24 leaves) were grown in clay pots with a diameter of 9 squares, and when they reached the 1-leaf stage, the test compound was sprayed at a predetermined concentration (10 ml of the prepared chemical solution) using a spray gun. After leaving it in a greenhouse at 24-25°C for a day and night, discs (agar punching) of Botrytis cinerea, which had been cultured in advance on potato-dextrose agar (PDA medium), were placed on cucumber leaves and inoculated. On the third day thereafter, the lesion length was investigated, and the lowest effective concentration corresponding to a control value of 100 was determined in the same manner as in Test Example 1 above.

Table 4 Test Example 4 Cucumbers (variety: Yotsuba) were cultivated in clay pots with a diameter of 9α, and when they reached the two-leaf stage, 20 m of leaf liquid prepared with the test compound at a predetermined concentration was sprayed using a spray gun. did. 2
After being left in a greenhouse at 4 to 25°C for a day and night, it was inoculated by spraying with a downy mildew spore suspension. On the fifth day after inoculation, the number of lesions on the first leaf was investigated, and the lowest effective concentration corresponding to a control value of 100 was determined in the same manner as in Test Example 1 above.

Table 5 Test Example 6 Seedlings of oat (variety: Shingen) at the two-leaf stage were sprayed with a chemical solution of a prescribed concentration and left to dry in a greenhouse (for 11 days). The spores were inoculated and kept in a greenhouse at 20°C for 24 hours and then in a greenhouse for 10 days.
We investigated the degree of disease onset and determined the lowest effective concentration at which no disease onset was observed.

Table 6 Test Example 7 In Test Example 3, +1) 'J coral (variety Nistar King, Delicious) was used, and when it reached the 3-leaf stage, it was treated with a chemical solution; Inoculation by spraying liquid, as well as keeping it in a greenhouse for 2 days after inoculation (
After storage, the number of lesions was investigated on the 20th day, and the control value was 10.
The test was conducted in a similar manner except that the lowest effective concentration corresponding to 0 was determined. As a result, the minimum effective concentration of the compound of the present invention was 1d 31.5 ppm.

Formulation example 1 (a) 2/-6'-dichloro-4'-trifluoromethyl 2,6-sinitro 3-chloro-4-trifluoromethyldiphenylamine 20M parts (b) Di-cryte 72 parts by weight E→
8 parts by weight or more of sodium ligninsulfonate were uniformly mixed to prepare an irrigation agent.

Formulation Example 2 (a) 2',6'-dichloro-4'-trifluoromethyl 2,6-sinitro 3-chloro-4-trifluoromethyldiphenylamine 5 parts by weight (b) Talc 95 parts by weight or more homogeneously It was mixed to make a powder.

Formulation Example 3 (a) 2',6'-dichloro-4'-trifluoromethyl 2,6-sinitro 3-chloro-4-trifluoromethyldiphenylamine 20 parts by weight (b) Xylene 60 parts by weight (c) Polyoxy Ethylene alkylaryl ether
20 parts by weight or more of each component were mixed and dissolved to form an emulsion.

Formulation example 4 (a) 78 parts by weight of Sikurite (b)
Labelin S (Product name: Dai-Kogyo Seiyaku Co., Ltd.) 2 parts by weight (c) Solgale 5039 (Product name: Toho Chemical Co., Ltd. #
) Carplex (trade name: Shionogi & Co., Ltd.) A mixture of at least one part of each component of the 15-fold phase and 2', '6/-dichloro4
'-)lifluoromethyl2,6-sinitro3-chloro-4-)! , +fluoromethyldiphenylamine and'
k, mixed at an electric storage ratio of 4:1 and used as an irrigation agent.

Patent applicant: Ishihara Sangyo Co., Ltd. 373-

Claims (1)

[Claims] 1,2',6'-dichloro-4'-trifluoromethyl2,6-sinitro3-chloro-4-trifluoromethyldiphenylamine2,2',6'-dichloro-4'- A pest control agent comprising trifluoromethyl 2,6-sinitro-3-chloro-4-trifluoromethyldiphenylamine t,'ff as an active ingredient.